CN1146643C - Flame-retardant thermoplastic composition with improved properties - Google Patents
Flame-retardant thermoplastic composition with improved properties Download PDFInfo
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- CN1146643C CN1146643C CNB008159645A CN00815964A CN1146643C CN 1146643 C CN1146643 C CN 1146643C CN B008159645 A CNB008159645 A CN B008159645A CN 00815964 A CN00815964 A CN 00815964A CN 1146643 C CN1146643 C CN 1146643C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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Abstract
The invention relates to a flame-retardant thermoplastic composition which comprises at least (A) a thermoplastic polymer and (B) a flame-retardant system and which also contains (C) an n-alkanelactam-substituted polymer. Such a composition shows both a good flame retardancy, in particular a short afterflame time and little dripping, and also excellent mechanical properties. In particular, the n-alkanelactam-substituted polymer is a polyolefine, substituted with n-alkanelactam groups, with n being chosen from between 2 and 12. More in particular, the n-alkanelactam is polyvinyl pyrrolidone. Preferably, the thermoplastic polymer is a polycondensation polymer, in particular a polyamide, a polyester or a polycarbonate. Particularly suitable for use as the polyamide are PA-6, PA-6,6, PA-4,6 and semi-aromatic polyamides. The flame-retardant system may be both a halogen-containing and a halogen-free system. Preferably, the flame-retardant system comprises a halogen-containing compound and an antimony-containing compound.
Description
Technical field
The present invention relates to flame-retardant thermoplastic compositions, described composition comprises: (A) thermoplastic polymer and (B) flame-retardant system.
Background technology
This composition can be specifically referring to WO-95/18178 (DuPont), and this patent has been described and adopted the daiamid composition that contains bromination polystyrene and sodium antimonate combination as flame-retardant system.Except the polymeric amide (as aromatic poly) of for example Wholly aromatic, thermoplastic polymer itself is not sufficient to fire-retardant usually, and therefore thermoplastic polymer is used in combination with the flame-retardant system of being made up of one or more fire retardants and one or more synergistic agent (promptly promoting the compound of flame retardant resistance) in the practice.
The shortcoming of this composition is that flame-retardant system is to composition properties, particularly mechanical property, thermal characteristics, electrical property and processing characteristics have negative impact, and the amount of used flame-retardant system is the compromise amount of required mechanical property, thermal characteristics, processing characteristics and electrical property of desired flame retardant resistance (as meeting the V0 level that Underwriters Laboratories UL-94 tests) and composition.For example the existence of ANTIMONY TRIOXIDE SB 203 99.8 PCT causes the thermal destruction of composition under high processing temperature (the particularly temperature more than 280 ℃), wherein also causes decolouring, makes mould fouling and corrosion processing equipment.In the practice, in thermoplastic compounds, use a small amount of as far as possible flame-retardant system, and its dropping liquid (dripping) is to a certain degree accepted for the UL-94 test.
Summary of the invention
Therefore target of the present invention provides particularly at high temperature, more especially has the thermoplastic compounds of good flame-retardance energy, thermal characteristics, processing characteristics and mechanical property under the high temperature more than 280 ℃.
The inventor finds to comprise at least uncannily: (A) thermoplastic polymer and (B) flame-retardant system, and (C) flame-retardant thermoplastic compositions of the polymkeric substance that replaces of n-paraffinic hydrocarbons lactan shows and has excellent flame-retardant performance simultaneously (Duan residual flame time particularly, more especially always residual flame time) and good mechanical property.After the residual flame time being defined as stopping to use flame according to the UL-94 test, sample is burned to the time of extinguishing.Total residual flame time is the assembly time (t of 5 samples
1+ t
2), t wherein
1For using for the first time the residual flame time behind the flame, t
2For using for the second time the residual flame time behind the flame.
As another advantage of the present composition, discovery can greatly reduce the dropping liquid of UL-94, and the composition that also contains glass fibre of the present invention is especially true.Based on the strict demand that fire-retardant combination is improved constantly, need most few dropping liquid, dropping liquid does not preferably take place.
Another advantage of the present composition is to reduce the amount of synergistic agent under the situation that does not have the negative impact flame retardant resistance, particularly is reduced in the amount of antimony compounds in the halogen-containing flame-retardant system.As a result, can obtain to contain the composition of less synergistic agent, particularly less antimony compounds, they have good especially flame retardant properties simultaneously.
Another advantage of the present composition is that the situation of the composition decolouring that for example at high temperature takes place during processing compositions can for example reduce by the amount that reduces synergistic agent.
From EP-A-401,740 (DuPont, USA) know intensity behind aging under the performance, particularly fibre strength of in to Kevlar, using Polyvinylpyrolidone (PVP) (PVP) to be improved, impressionability, UV stable, the heat affecting and the binding property in matrix material as additive.By the PVP (with respect to always forming calculating) of about 11% weight with the fabric that the fiber of aromatic poly preparation is made is also shown the better patience of (NFPA (NFPA) experimental technique 1971,5-1 part) irradiation heat that fiber is exposed.Described document does not mention that the dropping liquid performance of composition, particularly PVP concentration are equal to or less than the dropping liquid performance of 10% weight (calculating with respect to composition total weight).
From US-5,236,982 people such as () Cossement PVP as can be known are used as the additive of fiberglass surfacing layer, and it is mixed in the thermoplastic polymer subsequently to obtain glass fibre enhanced thermoplastic compounds.Common about 0.008% weight of the concentration of PVP (calculating) in composition with respect to total composition.According to aforementioned documents, PVP is used as the key property that lubricant keeps used glass fibre, as the length and the amount of particulate.
In the application's specification sheets, the polymkeric substance that n-paraffinic hydrocarbons lactan replaces be interpreted as contain a large amount of by lactan the N atom and the polymkeric substance of the n-paraffinic hydrocarbons lactan group of polymer-bound.What be suitable as n-paraffinic hydrocarbons lactan group is group derived from n-paraffinic hydrocarbons lactan, and wherein n-is integer and n＞1, particularly is selected from 2 groups to the n-paraffinic hydrocarbons lactan of the integer that reaches as high as 12 (comprising 12) derived from n wherein.More particularly, described n-paraffinic hydrocarbons lactan is 2-ethane lactan (ethylenimine-2-ketone), 3-propane lactan (azetidinone), 4-butane lactan (butyrolactam or 2-Pyrrolidone), γ-Valerolactim, 5-pentane lactan (δ-Valerolactim), 3-methylpent lactan, 6-methylpent lactan, 6-hexane lactan (ε-Ji Neixianan), 7-heptane lactan (φ-oenantholactam), 8-octane lactan (γ-spicy inner formyl amine), 9-nonane lactan (θ-ninth of the ten Heavenly Stems lactan), 10-decane lactan (ω-caprinolactam), 11-undecane lactan or 12-dodecanoic lactam (omega-lauric lactam).
The polymkeric substance that can select any aliphatic series or aromatic(based)polymer to replace as n-paraffinic hydrocarbons lactan.Particularly, described polymkeric substance is a polyolefine, as polyethylene, polypropylene or its multipolymer.Described n-paraffinic hydrocarbons lactan group can be identical or different polymer molecule independently separately.
Specifically, the polymkeric substance that replaces of the described n-paraffinic hydrocarbons lactan compound that the unit that meets formula 1 is formed of serving as reasons:
-(CR
1R
2)- (1)
R in the formula
1And R
2Independent separately is H or n-paraffinic hydrocarbons lactan group, and condition is that each molecule comprises at least one n-paraffinic hydrocarbons lactan group.The polymkeric substance that preferred described n-paraffinic hydrocarbons lactan replaces is Polyvinylpyrolidone (PVP) (PVP).The Polyvinylpyrolidone (PVP) of several molecular weight can Luviskol
The trade(brand)name of (BASF, Germany) is purchased and can be obtained by the linear polymerization of monomer N-vinyl-2-Pyrrolidone.Polyvinylpyrolidone (PVP) is made of the unit that meets formula 2:
In fact the present composition can use the polymkeric substance of the n-paraffinic hydrocarbons lactan replacement with any molecular weight.Described molecular weight can change in wide region, specifically can be from about 7,000 to about 2,000,000.Preferably be chosen in about 45,000 to about 2,000,000 molecular weight.Can freely select the amount of the polymkeric substance of n-paraffinic hydrocarbons lactan replacement.Preferably with respect to the weight of described thermoplastic polymer, described consumption is a 0.01-10% weight, and preferred described consumption is a 0.1-5% weight.The polymkeric substance that the n-paraffinic hydrocarbons lactan of the present invention definition replaces also comprises the polymkeric substance that the n-paraffinic hydrocarbons lactan that contains small amount of impurities or unreacted monomer replaces, for example have a small amount of as 1% weight is following (with respect to as described in the weight calculating of the polymkeric substance that replaces of n-paraffinic hydrocarbons lactan) the PVP of 2-Pyrrolidone.
The thermoplastic polymer that any those skilled in the art were familiar with all can be used as the thermoplastic polymer (A) in the present composition.Preferred polycondensate, particularly polyester, polycarbonate or the polymeric amide selected.
The example of the polyester that is fit to has the copolyester of poly terephthalic acid (ring) alkylene ester or itself and m-phthalic acid, as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly terephthalic acid cyclohexylidene dimethylene ester (PCT); Poly-alkylene naphthalate is as PEN (PEN), poly-naphthalic acid propylene glycol ester (PPN) and PBN (PBN); Poly-dibenzoic acid alkylene ester, as poly-dibenzoic acid second diester and as described in the copolyester of polyester.Preferred PET, PBT, PEN or the PBN of selecting.Same be fit to also have the block copolymerization polyester, described copolyester also comprises the soft polyester chain link derived from least a polyethers or aliphatic polyester except being selected from aforementioned group hard polyester chain link.The example of this rubber-like block copolymerization polyester is described in John Wiley ﹠amp; 75 pages of the 8th chapters (1996 that play " thermoplastic elastomer (the Thermoplastic Elastomers) " of (1988) and Hanser Verlag publication of 12 volumes of " polymer science and engineering encyclopedia (the Encyclopedia of Polymer Scienceand Engineering) " that Sons company publishes, second edition), its associated viscera is interpreted as and addresses.
The example of the polymeric amide that is fit to has aliphatic polyamide, as PA-6, PA-6, and 6, PA-9, PA-11, PA-4,6; Polymeric amide and copolyamide thereof based on 2 methyl pentamethylenediamine and hexanodioic acid; Based on the semiaromatic polyamide composition of aromatic dicarboxylic acid (as m-phthalic acid and terephthalic acid) and aliphatic diamine (as hexanediamine), as PA-6/T, PA-6.6/T, PA-6/6.T, PA-6,6/6, T, PA-6,6/6/6, T, PA-6T/6I, PA-6,6/6, I/6, T and PA-6,6/2-MPMD, 6, and fully aromatic polyamide, PA=polymeric amide wherein, the T=terephthalic acid, I=m-phthalic acid, MPMD=2-methyl amyl methylene diamine.
Particularly, described thermoplastic polymer has and is equal to or higher than 280 ℃ fusing point.
Find uncannily that now composition of the present invention can and tangible chemical degradation not take place in the following processing of higher temperature (particularly being higher than 280 ℃).This polymkeric substance that makes n-paraffinic hydrocarbons lactan replace is particularly suitable at the dystectic thermoplastic polymer of tool, as using in polymeric amide-4,6 and the semiaromatic polyamide composition.Preferred polymeric amide is selected from PA-6, PA-6, and 6, PA-4,6 and semiaromatic polyamide composition.
Composition of the present invention comprises flame-retardant system (B), particularly comprises the halogen-containing system that comprises at least a halogen contained compound.Be suitable as the system that for example contains as the halogen-containing flame retardant of fire retardant that has of halogen-containing system, brominated Polystyrene for example is as can be available from the Pyrochek of FerroCorporation (USA)
68PB and can be available from the Saytex of Albemarle (USA)
HP 7010; The bromination polyphenylene ether is as can be available from the PO64P of Great Lakes (USA)
Poly-Dowspray 9 is as can be available from the PDBS80 of Great Lakes
Poly-tribromo-benzene ethene; Poly-pentabromobenzene ethene; Polydichlorostyrene; Poly-trichlorobenzene ethene; Poly-pentachlorobenzene ethene; Poly-three bromo-Alpha-Methyl-vinylbenzene; Poly-two bromo-p-phenylenes; Poly-three bromo-p-phenylenes; Poly-two chloro-p-phenylenes; Poly-bromo-is right-phenylate; Poly-bromo-neighbour-phenylate; Vinylformic acid pentabromo-benzyl ester is as the FR1025 available from AmeriBrom (USA)
Ethylenebis (tetrabromo phthalimide) is as the Saytex available from Albemarle (USA)
BT-93W; Poly-bromo biphenyl; Contain bromination phenoxy group and chloride fire retardant, as DeChlorane
(Occidental Chemical Corporation is USA) with other brominated compound, as the Saytex available from Albemarle (USA)
8010.
Described flame-retardant system also can comprise synergistic agent.The synergistic agent that is fit to has:
-antimony containing compounds is as ANTIMONY TRIOXIDE SB 203 99.8 PCT such as Bluestar
RG (Campine, Belgium), four weisspiessglanzs, antimony pentaoxide, sodium antimonate such as Pyrobloc
SAP-2 (Cookson SpecialtyAdditives), antimony tartrate;
-zinc borate is as Firebrake
ZB (Borax Inc., USA);
-magnesium hydroxide, aluminium hydroxide, ferric oxide, zinc oxide, calcium oxide and similar substance.
Especially, described halogen-containing system contains antimony containing compounds.
Also can select the halogen-free flame-retardant system as described flame-retardant system.The halogen-free flame-retardant that is fit to has:
-containing metal compound is as magnesium hydroxide and aluminium hydroxide;
-nitrogenous compound is as melamine, melamine cyanurate (melamine cyanurate), melam, melem, melon;
-P contained compound is as red phosphorus, melamine phosphate, Tripyrophosphoric acid melamine Melapur for example
200 (DSM, Holland) and PMP-100
(Nissan Chemical Industries, Japan), Tripyrophosphoric acid melam such as PMP-200
(Nissan Chemical Industies), Tripyrophosphoric acid melem such as PMP-300
(Nissan Chemical Industies), phosphonitrile based compound and ammonium polyphosphate.
Composition of the present invention also can comprise and is generally used for polymer composition and is other additive that those skilled in the art were familiar with, condition is that they can not impair the present invention basically, and described additive specifically has reagent, nucleator, tenderizer, ultra-violet stabilizer and the thermo-stabilizer etc. of pigment, processing aid such as releasing agent, accelerate crystallisation.Also can choose adding wantonly and promote other fire-retardant material, for example become the material (as fluoropolymer, as tetrafluoroethylene) of carbon species (as polyphenylene oxide and polycarbonate) and the behavior of change dropping liquid.Composition of the present invention specifically can comprise mineral filler or toughener.The mineral filler or the toughener that are suitable for can be all fillers that those skilled in the art are familiar with, for example glass fibre, steel fiber, graphite fibre, Kevlar, granulated glass sphere, pure aluminium silicate, asbestos, mica, clay, calcined clay and talcum.The preferred glass fibre of selecting.
Preferred composition of the present invention comprises:
A) thermoplastic polymer of 40-90% weight is selected from polymeric amide, polycarbonate and polyester;
B) the halogen-containing flame-retardant system of 10-40% weight;
C) 0.1-5% weight has 45,000 to 2,000, the Polyvinylpyrolidone (PVP) of 000 molecular weight;
D) glass fibre of 0-50% weight;
E) other additive of 0-20% weight;
Wherein (A+B+C+D+E) equals 100% weight.
Thermoplastic compounds of the present invention simply mode obtains by melting mixing.The preferred use is furnished with the forcing machine that all required components is fed to the device in the forcing machine (be sent to the opening for feed of forcing machine or be sent in the melt).According to a kind of embodiment, the polymkeric substance that described n-paraffinic hydrocarbons lactan replaces can constitute the part of flame-retardant system B.In another embodiment, the polymkeric substance of described n-paraffinic hydrocarbons lactan replacement can directly be fed in the melt separately or can at first mix with polymer beads.
Composition of the present invention is applicable to article, particularly film, fiber, sheet material and the mo(u)lded item that any those skilled in the art of preparation are familiar with.
To further come the present invention is made an explanation by the following examples and Comparative Examples.
Embodiment
Embodiment
Example I-XII and Comparative Examples A-E
Component prepares various compositions below using:
(A) thermoplastic polymer:
● polymeric amide 4,6:Stanyl
KS200, DSM N.V., Holland,
● polyamide 6,6/6T:Grivory
FE 5011, EMS Chemie. Switzerland,
● polyester PBT:Arnite
T04200, DSM N.V., Holland,
● polyamide 6: Akulon
K122, DSM N.V., Holland;
(B) flame-retardant system
● Pyrochek
68PBi (brominated Polystyrene-Ferro Corp., USA),
● PDBS80
(poly-Dowspray 9-Great Lakes, USA),
● Saytex
BT-93W (ethylenebis (tetrabromo phthalimide)-Albemarle, USA),
● GR2617
(Sb
2O
3, as a kind of 80%Sb that contains
2O
3PA-6 master batch-Campine, Belgium),
● GR2616
(Sb
2O
3, as a kind of 80%Sb that contains
2O
3PBT master batch-Campine, Belgium),
● Saytex
HP-7010 (brominated Polystyrene-Albemarle, USA),
●Saytex
8010(Albemarle，USA)；
(C) Polyvinylpyrolidone (PVP)
● Luviskol
K90 (BASF, Germany), Mw=1,200,000-2,000,000,
● Luviskol
K30 (BASF, Germany), Mw=45,000-55,000,
● Luviskol
K17 (BASF, Germany), Mw=7,000-11,000;
Glass fibre:
●OC173X-10C
(Owens-Corning，USA)，
●OC183-11C
(Owens-Corning，USA)；
Lubricant: AC540A
(Allied, USA);
Stablizer: Irganox
1098 (Ciba Geigy, Switzerland);
Filler: Stealene (talcum, Luzenac, France).
Described composition is listed in the table 1,3,5,7 and 9.All amounts all are the weight percents that calculate corresponding to total composition.All compositions all prepare by fusion.
The flame retardant resistance according to UL-94 of all compositions (classification, total residual flame time), dropping liquid performance (representing with the dropping liquid sample number) and mechanical property all use 5 sample rods to measure.The results are summarized in the table 2,4,6,8 and 10.Be determined under the working pressures of 900 crust, the length of polymer flow is as the helical degree of mobilization in the bandlet type coil (flatspiral) of the wide and 1mm cross section of the 15mm on being fixed in Arburg CMD injection moulding machine.
Discuss
Comparative Examples A and example I, II and III comparison shows that a little P VP causes the obvious decline (reaching as high as 50%) of total residual flame time and drip does not take place fully in composition of the present invention.Mechanical property, particularly Young's modulus, tensile strength, elongation at break, notched impact strength and helical degree of mobilization remain unchanged or improve, and particularly tensile strength remains unchanged or improves.
The comparison of the comparison of the comparison of comparative example B and EXAMPLE IV and V, comparative example C and example VI and VII, comparative example D and example VII A I and comparative example E and example I X comparison shows that when reducing synergistic agent concentration in the presence of a certain amount of PVP, mechanical property, particularly tensile strength and elongation at break then raise, and total residual flame time keeps constant substantially; Drip does not take place in these compositions of the present invention fully yet.
Embodiment X, XI and XII (table 7 and 8) show that flame retardant effect of the present invention does not depend on the molecular weight of PVP.But for lower molecular weight, particularly the molecular weight below 10,000 can increase concentration, and those skilled in the art can be by the combination of simple optimized choice molecular weight and concentration.When with the concentration repeated experiments XII of 6% weight, its flame retardant resistance can match in excellence or beauty with embodiment X and XI.
Table 1:PA-4,6 compositions
| Component | A | I | II | III | B | IV | V | C | VI | VII |
| Polymkeric substance Stanyl KS200 | 42.74 | 42.49 | 42.24 | 41.74 | 41.00 | 43.00 | 44.00 | 32.84 | 34.64 | 35.59 |
| Fire retardant Pyrochek 68PBi PDBS80 GR2617 | 18.75 - 7.81 | 18.75 - 7.81 | 18.75 - 7.81 | 18.75 - 7.81 | - 21.00 7.50 | - 21.00 5.00 | - 21.00 3.75 | - 19.50 7.00 | - 19.50 4.70 | - 19.50 3.50 |
| PVP Luviskol K90 | - | 0.25 | 0.50 | 1.00 | - | 0.50 | 0.75 | - | 0.50 | 0.75 |
| Glass fibre OC173X-10C | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 40 | 40 | 40 |
| Lubricant and stablizer | 0.70 | 0.70 | 0.70 | 0.70 | 0.50 | 0.50 | 0.50 | 0.66 | 0.66 | 0.66 |
Table 2: the character of table 1 composition
| Character | Unit | ISO | A | I | II | III | B | IV | V | C | VI | VII |
| Mechanical property Young's modulus tensile strength elongation at break notched impact strength (IZCD) helical degree of mobilization (900 crust) | GPa MPa ％ KJ/m 2cm | 527/1A 527/1A 527/1A 180/1A | 11.6 172 2.3 10.6 102 | 11.5 183 2.4 10.4 95 | 11.4 179 2.3 10.3 103 | 11.6 181 2.2 9.3 100 | 11.3 150 1.8 12.2 127 | 11.3 165 1.9 11.5 128 | 11.3 176 2.1 11.6 127 | 15.0 161 1.5 15.7 115 | 15.4 180 1.6 13.9 113 | 15.4 186 1.7 16.1 117 |
| 48 hours/23 ℃/50%R.H. classification of thick sample 125 * 13 * 0.8mm of UL94V 0.8mm, 168 hours/70 ℃ total residual flame time of classification of dropping liquid sample of total residual flame time dropping liquid sample | Second second | V0 21 1 V0 23 1 | V0 13 0 V0 24 0 | V0 10 0 V0 12 0 | V0 10 0 V0 12 0 | V0 24 4 V0 31 5 | V0 23 0 V0 16 0 | V0 28 0 V0 39 0 | V0 10 0 V0 10 0 | V0 10 0 V0 10 0 | V0 9 0 V0 10 0 |
Table 3:PA-6, the 6/6T composition
| Component | D | VIII |
| Polymkeric substance Grivory FE5011 | 42.87 | 42.27 |
| Fire retardant Pyrochek 68PBi GR2617 | 18.75 7.81 | 18.75 3.91 |
| PVP Luviskol K90 | - | 0.50 |
| Glass fibre OC173X-10c | 30 | 30 |
| Lubricant and stablizer | 0.57 | 0.57 |
Table 4: the character of table 3 composition
| Character | Unit | ISO | D | VIII |
| Mechanical property Young's modulus tensile strength elongation at break notched impact strength (IZCD) helical degree of mobilization (900 crust) | GPa MPa ％ KJ/m 2mm | 527/1A 527/1A 527/1A 180/1A | 12.5 178 2.0 10.1 120 | 12.4 188 2.1 10.1 120 |
| Thick sample 125 * 13 * 0.8mm of UL94V0.8mm 48 hours/23 ℃/50%R.H.Dropping liquid sample of total residual flame time of classification 168 hours/70 ℃Dropping liquid sample of total residual flame time of classification | Second second | V0 10 1 V0 10 0 | V0 14 0 V0 10 0 |
Table 5:PBT composition
| Component | E | IX |
| Polymer A rnite TO4200 | 56 | 57.5 |
| Fire retardant Saytex BT-93W GR2616 | 9 5 | 9 2.5 |
| PVP Luviskol K90 | - | 1.0 |
| Glass fibre OC183-11c | 30 | 30 |
Table 6: the character of table 5 composition
| Character | Unit | ISO | D | VIII |
| Thick sample 125 * 13 * 2mm of UL94V 2mm 48 hours/23 ℃/50%R.H.Dropping liquid sample of total residual flame time of classification 168 hours/70 ℃Dropping liquid sample of total residual flame time of classification | Second second | V0 10 0 V0 10 0 | V0 10 0 V0 10 0 |
Table 7: the PA-4 of the different amount of tool PVP, 6 compositions
| Component | X | XI | XII |
| Polymkeric substance Stanyl KS200 | 44 | 44 | 44 |
| Fire retardant PDBS80 GR2617 | 21 3.75 | 21 3.75 | 21 3.75 |
| PVP Luviskol K90 Luviskol K30 Luviskol K17 | 0.75 - - | - 0.75 - | - - 0.75 |
| Glass fibre OC 173X-10C | 30 | 30 | 30 |
| Lubricant and stablizer | 0.50 | 0.50 | 0.50 |
Table 8: the character of table 7 composition
| Character | Unit | ISO | X | XI | XII |
| Mechanical property Young's modulus tensile strength elongation at break notched impact strength (IZCD) | GPa MPa ％ KJ/m 2 | 527/1A 527/1A 527/1A 180/1A | 11.2 181 2.2 11.1 | 11.1 181 2.3 10.9 | 11.2 174 2.1 11.8 |
| Thick sample 125 * 13 * 0.8mm of UL94V 0.8mm 48 hours/23 ℃/50%R.H.Dropping liquid sample of total residual flame time of classification 168 Hour/70℃ dropping liquid sample of total residual flame time of classification | Second second | V0 22 0 V0 22 1 | V0 28 0 V0 24 0 | V0 55 5 V2 51 5 |
Table 9:PA-6 composition
| Component | F | XIII | G | XIV |
| Polymer A kulon K122 | 44.45 | 46.02 | 53.1 | 54.65 |
| Fire retardant Saytex HP7010 Saytex 8010 GR2617 | 20.6 - 4.15 | 20.6 - 2.08 | - 12 4.1 | - 12 2.05 |
| PVP Luviskol K90 | - | 0.5 | - | 0.5 |
| Glass fibre OC 173X-10c | 30 | 30 | - | - |
| Filler Stealene | - | - | 30 | 30 |
| Other additive | 0.8 | 0.8 | 0.8 | 0.8 |
Table 10: the character of table 9 composition
| Character | Unit | ISO | F | XIII | G | XIV |
| Mechanical property Young's modulus tensile strength elongation at break notched impact strength (IZCD) | GPa MPa ％ KJ/m 2 | 527/1A 527/1A 527/1A 180/1A | 10.7 148 2.5 - | 11.6 152 2.2 - | 7.4 69 1.6 - | 7.5 66 1.3 - |
| Thick sample 125 * 13 * 0.8mm of UL94V 0.8mm 48 hours/ 23℃/50％R.H. (5 sample rod) dropping liquid sample number 168 is little total residual flame time of classification Time/70 ℃(5 sample rod) dropping liquid sample number of total residual flame time of classification | Second second | V0 45 100％ V0 38 100％ | V0 10 100％ V0 10 100％ | V2 13 100％ V2 15 100％ | V2 20 100％ V2 18 100％ |
Claims (11)
1. flame-proofed thermoplastic daiamid composition, described flame-retardant thermoplastic compositions comprises at least based on a kind of polyamide thermoplastic of total composition meter: 40-90wt% (A) and a kind of flame-retardant system of 10-40wt% (B), it is characterized in that: described composition also comprises the polymkeric substance based on (C) n-paraffinic hydrocarbons lactan replacement of total composition meter 0.01-10wt%.
2. the flame-proofed thermoplastic daiamid composition of claim 1 is characterized in that: the molecular weight of the polymkeric substance that described n-paraffinic hydrocarbons lactan replaces is 7,000 to 2,000, between 000.
3. claim 1 or 2 flame-proofed thermoplastic daiamid composition, it is characterized in that: the polyolefine of the polymkeric substance that described n-paraffinic hydrocarbons lactan replaces for replacing with n-paraffinic hydrocarbons lactan group, n is selected from 2 to 12.
4. the flame-proofed thermoplastic daiamid composition of claim 3 is characterized in that: the polymkeric substance that described n-paraffinic hydrocarbons lactan replaces is a Polyvinylpyrolidone (PVP).
5. claim 1 or 2 flame-retardant thermoplastic compositions, it is characterized in that: described polyamide thermoplastic is selected from PA-6, PA-6, and 6, PA-4,6 and partially aromatic polyamide.
6. claim 1 or 2 flame-proofed thermoplastic daiamid composition, it is characterized in that: described flame-retardant system comprises at least a halogen contained compound and a kind of antimony containing compounds.
7. claim 1 or 2 flame-proofed thermoplastic daiamid composition is characterized in that: also have mineral filler.
8. the flame-proofed thermoplastic daiamid composition of claim 7, it is characterized in that: described filler is a glass fibre.
9.n-the polymkeric substance that the paraffinic hydrocarbons lactan replaces comprises purposes in the flame retardant properties of polyamide thermoplastic compositions of at least a polyamide thermoplastic (A) and a kind of flame-retardant system (B) in improvement.
10. halogen-containing flame-proofed thermoplastic daiamid composition, described composition comprises:
A) polyamide thermoplastic of 40-90% weight,
B) the halogen-containing flame-retardant system of 10-40% weight,
C) 0.1-5% weight has 45,000 to 2,000, the Polyvinylpyrolidone (PVP) of 000 molecular weight,
D) glass fibre of 0-50% weight,
E) other additive different of 0-20% weight with A, B, C or D,
Wherein (A+B+C+D+E) equals 100% weight.
11. film, fiber or mo(u)lded item, described goods can use the composition of claim 1 or 2 or the composition of claim 10 to obtain.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL1013134A NL1013134C2 (en) | 1999-09-24 | 1999-09-24 | Flame retardant thermoplastic composition with improved properties. |
| NL1013134 | 1999-09-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1391598A CN1391598A (en) | 2003-01-15 |
| CN1146643C true CN1146643C (en) | 2004-04-21 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB008159645A Expired - Fee Related CN1146643C (en) | 1999-09-24 | 2000-09-12 | Flame-retardant thermoplastic composition with improved properties |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US6951896B2 (en) |
| EP (1) | EP1232217B1 (en) |
| JP (1) | JP4717307B2 (en) |
| KR (1) | KR100681646B1 (en) |
| CN (1) | CN1146643C (en) |
| AT (1) | ATE274031T1 (en) |
| AU (1) | AU7561100A (en) |
| DE (1) | DE60013166T2 (en) |
| ES (1) | ES2225223T3 (en) |
| NL (1) | NL1013134C2 (en) |
| TW (1) | TWI256407B (en) |
| WO (1) | WO2001021711A1 (en) |
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| EP1479728A1 (en) * | 2003-05-22 | 2004-11-24 | DSM IP Assets B.V. | Flame retardant polyamide composition |
| US7202296B2 (en) * | 2003-12-19 | 2007-04-10 | Albemarle Corporation | Flame retardant compositions and their use |
| EP1681313A1 (en) * | 2005-01-17 | 2006-07-19 | DSM IP Assets B.V. | Heat stabilized moulding composition |
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| JP5577755B2 (en) * | 2010-03-04 | 2014-08-27 | 東レ株式会社 | Polyester resin composition |
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| US20130029151A1 (en) * | 2011-03-18 | 2013-01-31 | E. I. Du Pont De Nemours And Company | Flame-resistant finish for inherently flame resistant polymer yarns and process for making same |
| CN110079078A (en) * | 2011-06-09 | 2019-08-02 | 索尔维特殊聚合物美国有限责任公司 | Daiamid composition characterized by improved thermal stability |
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| JP6386652B2 (en) * | 2017-12-13 | 2018-09-05 | 三菱エンジニアリングプラスチックス株式会社 | Method for producing thermoplastic resin composition |
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-
1999
- 1999-09-24 NL NL1013134A patent/NL1013134C2/en not_active IP Right Cessation
-
2000
- 2000-09-12 WO PCT/NL2000/000647 patent/WO2001021711A1/en active IP Right Grant
- 2000-09-12 AU AU75611/00A patent/AU7561100A/en not_active Abandoned
- 2000-09-12 JP JP2001525277A patent/JP4717307B2/en not_active Expired - Fee Related
- 2000-09-12 EP EP00964776A patent/EP1232217B1/en not_active Expired - Lifetime
- 2000-09-12 ES ES00964776T patent/ES2225223T3/en not_active Expired - Lifetime
- 2000-09-12 KR KR1020027003821A patent/KR100681646B1/en not_active IP Right Cessation
- 2000-09-12 CN CNB008159645A patent/CN1146643C/en not_active Expired - Fee Related
- 2000-09-12 DE DE60013166T patent/DE60013166T2/en not_active Expired - Lifetime
- 2000-09-12 AT AT00964776T patent/ATE274031T1/en not_active IP Right Cessation
- 2000-09-15 TW TW089119000A patent/TWI256407B/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| JP4717307B2 (en) | 2011-07-06 |
| US6951896B2 (en) | 2005-10-04 |
| JP2003510396A (en) | 2003-03-18 |
| EP1232217A1 (en) | 2002-08-21 |
| KR20020040816A (en) | 2002-05-30 |
| EP1232217B1 (en) | 2004-08-18 |
| NL1013134C2 (en) | 2001-03-27 |
| KR100681646B1 (en) | 2007-02-09 |
| DE60013166T2 (en) | 2005-09-08 |
| US20030055152A1 (en) | 2003-03-20 |
| ATE274031T1 (en) | 2004-09-15 |
| TWI256407B (en) | 2006-06-11 |
| CN1391598A (en) | 2003-01-15 |
| ES2225223T3 (en) | 2005-03-16 |
| AU7561100A (en) | 2001-04-24 |
| WO2001021711A1 (en) | 2001-03-29 |
| DE60013166D1 (en) | 2004-09-23 |
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